Ring-opening hydrogenated copolymer and process for producing the same

ABSTRACT

There are disclosed a polycyclic norbornene or its derivative hydrogenated copolymer which contains 
     a repeating unit represented by the following formula [I] or the alkyl-substituted derivative thereof (A), 
     a repeating unit represented by the following formula [II] or the alkyl-substituted derivative thereof (B) and, as desired, 
     5-85% by mole of at least one repeating unit (C) selected from a repeating unit represented by the following formula [III], the alkyl-substituted derivative thereof, a repeating unit represented by the following formula [IV], the alkyl-substituted derivative and the alkylidene-substituted derivative thereof, and a process for producing the polycyclic norbornene or its derivative ring-opening hydrogenated copolymer ##STR1##  wherein ------ represents either a single bond or a double bond.

TECHNICAL FIELD

The present invention relates to a novel ring-opening hydrogenatedcopolymer excellent in thermal resistance, optical property andmoldability. In more particular, it relates to a polycyclic norborneneor its derivative ring-opening hydrogenated copolymer which is excellentin thermal resistance and gives moldings with little optical strain, anda process for producing the same.

BACKGROUND ART

Polymers hitherto mainly used as optical materials are polymethylmethacrylate and polycarbonate. However, the former has a problem ofrather high water absorption and the latter has a problem of developmentof birefringence in injection molding. Accordingly, it is becomingdifficult for these polymers to meet recent requirements, which arebecoming increasingly more severe.

in recent years, polymers which use polycyclic norbornene or alliedmonomers have been developed as polymeric materials improved in saidproperties in question. For example, Japanese Patent Application Kokai(Laid-open) No. 60-26024 describes that the hydrogenation products ofring-opening polymers of tetracyclodecenes or of ring-opening copolymersof tetracyclododecenes and norbornenes are excellent in transparency,water resistance and thermal resistance. However, the hydrogenationproducts of ring-opening polymers of tetracyclododecenes are not fullysatisfactory in moldability and their birefringence values are not sosmall as can meet the property requirement sufficiently. Thehydrogenation products of ring-opening copolymers of tetracyclododecenesand norbornenes also have similar problems. Although hydrogenationproducts of this kind having a high proportion of norbornenes incopolymerization of 40-50% by mole are somewhat improved in saidproperties, they have a low glass transition temperature (Tg) of95°-105° C. and hence their thermal resistance is not fullysatisfactory.

Japanese Patent Application Kokoku (Post-Exam. Publn.) No. 58-43412describes that the hydrogenation product of dicyclopentadienering-opening polymer can be easily heat-melt processed to give a tough,transparent sheet. The hydrogenation product, however, is unsatisfactoryin thermal resistance for use as optical disks because it has a lowglass transition temperature (Tg) of about 95° C.

On the other hand, polymers obtained by using polycyclic norbornene orallied monomers, when they have not been hydrogenated, are poor inresistance to oxidative degradation and hence unsuitable for use asoptical materials.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a novel polymericmaterial which is excellent in thermal resistance, optical property andmoldability.

Another object of the present invention is to provide a polycyclicnorbornene or its derivative ring-opening hydrogenated copolymer whichhas a high glass transition temperature and gives moldings with littleoptical strain.

The present inventors have made extensive study to develop a novelsynthetic resin suitable as optical polymer or as the raw materialthereof by using polycyclic norbornene or allied monomers. As the resultit has been found out that the hydrogenation products of ring-openingcopolymers obtainable by ring-opening copolymerization of (A)pentacyclopentadecadienes and/or pentacyclopentadecenes, (B)tetracyclododecenes and, as desired, (C) as least one monomer selectedfrom dicyclopentadienes, dihydrodicyclopentadienes and norbornenes areexcellent in thermal property and moldability and give moldings withlittle of optical strain. The present invention has been accomplished onthe basis of above finding.

BEST MODE FOR CARRYING OUT THE INVENTION

The first aspect of the present invention relates to a polycyclicnorbornene or its derivative ring-opening hydrogenated copolymer whichcontains

(A) 70-10% by mole of a repeating unit represented by the followingformula [I] or the alkyl-substituted derivative thereof, and

(B) 30-90% by mole of a repeating unit represented by the followingformula [II] or the alkyl-substituted derivative thereof, has anintrinsic viscosity [η] of 0.01-20 dl/g as determined in toluene at 25°C., and in which at least 50% of the (C------C) linkages constitutingthe main chain are single bonds ##STR2## wherein ------ representseither a single bond or a double bond.

The second aspect of the present invention relates to a polycyclicnorbornene or its derivative hydrogenated copolymer which contains

(A) preferably 85-5% by mole of a repeating unit represented by thefollowing formula [I] or the alkyl-substituted derivative thereof.

(B) preferably 10-90% by mole of a repeating unit represented by thefollowing formula [II] or the alkyl-substituted derivative thereof, and

(C) preferably 5-85% by mole of at least one repeating unit selectedfrom a repeating unit represented by the following formula [III], thealkyl-substituted derivative thereof, a repeating unit represented bythe following formula [IV], the alkyl-substituted derivative thereof orthe alkylidene-substituted derivative thereof, has an intrinsicviscosity [η] of 0.01-20 dl/g as determined in toluene at 25° C., and inwhich at least 50% of the (C------C) linkages constituting the mainchain are single bonds ##STR3## wherein ------ represents either asingle bond or a double bond.

The third aspect of the present invention relates to a process forproducing a polycyclic norbornene or its derivative hydrogenatedcopolymer wherein at least 50% of the (C------C) linkages constitutingthe main chain are single bonds which is characterized by hydrogenatingwith hydrogen and by use of a hydrogenation catalyst a part or the wholeof the olefinic unsaturated groups contained in a polycyclic norborneneor its derivative ring-opening copolymer which contains

(A) preferably 70-10% by mole of a repeating unit represented by thefollowing formula [I] or the alkyl-substituted derivative thereof and

(B) preferably 30-90% by mole of a repeating unit represented by thefollowing formula [II'] or the alkyl-substituted derivative thereof, andhas an intrinsic viscosity [η] of 0.01-20 dl/g as determined in tolueneat 25° C. ##STR4## wherein ------ represents either a single bond or adouble bond.

The fourth aspect of the present invention relates to a process forproducing a polycyclic norbornene or its derivative ring-openinghydrogenated copolymer wherein at least 50% of the (C------C) linkagesconstituting the main chain are single bonds which is characterized byhydrogenating with hydrogen and by use of a hydrogenation catalyst apart or the whole of the olefinic unsaturated groups contained in apolycyclic norbornene or its derivative ring-opening copolymer whichcontains

(A) preferably 85-5% by mole of a repeating unit represented by thefollowing formula [I'] or the alkyl-substituted derivative thereof,

(B) preferably 10-90% by mole of a repeating unit represented by thefollowing formula [II'] or the alkyl-substituted derivative thereof, and

(C) preferably 5-85% by mole of at least one repeating unit selectedfrom a repeating unit represented by the following formula [III° ], thealkyl-substituted derivative thereof, a repeating unit represented bythe following formula [IV'], the alkyl-substituted derivative thereof orthe alkylidene-substituted derivative thereof, and has an intrinsicviscosity [η] of 0.01-20 dl/g as determined in toluene at 25° C.##STR5## wherein ------ represents either a single bond or a doublebond.

The ring-opening copolymer used in the present invention employs as thecomponent monomer (A), among polycyclic norbornene and allied compounds,particularly4,9,5,8-dimethano-3a,4,4a,5,8,8a,9,9a-octahydro-1H-benzoindene (namely,pentacyclopentadecadiene),4,9,5,8-dimethano-2,3,3a,4,4a,5,8,8a,9,9a-decahydro-1H-benzoindene(namely, pentacyclopentadecene) or the alkyl-substituted derivativesthereof (hereinafter sometimes referred to as "component A") and, as thecomponent comonomer, (B) tetracyclododecenes, namely tetracyclododeceneand the alkyl-substituted derivatives thereof (hereinafter sometimesreferred to as "component B") and, as required, (C) at least one monomerselected from 4,7-methano-3a,4,7,7a-tetrahydro-1H-indene (namelydicyclopentadiene), 4,7-methano-2,3,3a,4,7,7a-hexahydroindene (namely,dihydrodicyclopentadiene), the alkyl-substituted derivatives thereof,and unsubstituted or substituted norbornene (hereinafter sometimesreferred to as "component C"), and can be prepared by known methods ofring-opening polymerization of cyclic olefins. The hydrogenationproducts of these ring-opening copolymers can be produced by usingconventional methods of hydrogenation.

The respective constituents of the present invention will be describedin detail below.

Monomer

The component A used in the present invention is selected from thefollowing two kinds of monomers. The first monomer ispentacyclopentadecadiene(4,9,5,8-dimethano-3a,4,4a,5,8,8a,9,9a-octahydro-1H-benzoindene)represented by the following formula [V] (said monomer being hereinafterabbreviated as "PCDE"). ##STR6##

Said PCDE may be obtained by subjecting cyclopentadiene to a Dieis-Alderreaction with dicyclopentadiene, followed by separation from thereaction mixture by such means as distillation.

The other monomer of the components A is pentacyclopentadecene(4,9,5,8-dimethano-2,3,3a,4,4a,5,8,8a,9,9a-decahydro-1H-benzoindene)represented by the following formula [VI] (hereinafter abbreviated as"PCPD"). ##STR7##

This compound may be prepared by subjecting cyclopentene to aDieis-Alder reaction with cyclopentadiene and then again subjecting thereaction product to a Dieis-Alder reaction with cyclopentadiene.

The PCDE and the PCPD mentioned above may be used either each alone oras a mixture of desired proportion.

The PCDE and the PCPD may be respectively the derivative thereofsubstituted with alkyl such as methyl, derivative thereof substitutedwith alkyl such as methyl, ethyl and propyl.

The components B used in the present invention are tetracyclododecene(hereinafter sometimes abbreviated as "TCD") represented by thefollowing formula [VII] or the alkyl-substituted derivative thereof.##STR8##

Said TCDs may be obtained by subjecting cyclopentadienes to aDieis-Alder reaction with norbornenes, followed by separation from thereaction mixture by such means as distillation.

The TCDs may be also the derivatives substituted with lower alkyl suchas methyl, ethyl and propyl. The alkyl substituent may be present alsoin plurality.

The components C used in the present invention are dicyclopentadiene(hereinafter sometimes abbreviated as "DCP"),2,3-dihydrodicyclopentadiene (4,7-methano-2,3,3a,4,7,7a-hexahydroindene,hereinafter sometimes abbreviated as "HDCP"), the derivatives thereofsubstituted with alkyl such as methyl, ethyl, propyl and butyl, orunsubstituted or substituted norbornene (hereinafter sometimesabbreviated as "NB"). These may be used each alone or as suitablemixtures thereof.

Examples of substituted norbornenes are alkyl-substituted norbornenessuch as 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene,5-ethyl-2-norbornene and 5-butyl-2-norbornene or alkylidene-substitutednorbornenes such as ethylidenenorbornene.

In the first and the third aspects of the present invention, thecomponent A mentioned above is used in a proportion of preferably 70-10%by mole, more preferably 60-20% by mole, and the component B in aproportion of preferably 30-90% by mole, more preferably 40-80% by mole.

In the second and the fourth aspects of the present invention thecomponent A is used in a proportion of preferably 85-5% by mole, morepreferably 70-10% by mole, the component B in a proportion of preferably10-90% by mole, more preferably 20-80% by mole, and the component C in aproportion of preferably 5-85% by mole, more preferably 10-70% by mole.

The use of the component A makes it possible to obtain a product whichcan give moldings with little optical strain even in the region ofhigher glass transition temperature as compared with the hydrogenationproduct of ring-opening copolymers of tetracyclododecenes (component B)with norbornenes (component C) known to the art. As the proportion ofthe component A used increases, the glass transition temperature rises.Too high a glass transition temperature is undesirable because it makesprocessing of the resin difficult. When the component A is not used, theglass transition temperature of the resulting polymer does not becomesufficiently high and, particularly when the polymer is hydrogenated forthe purpose of improving resistance to thermal degradation andphoto-degradation, the glass transition temperature decreases greatly ascompared with that of the original polymer, which is a problem inpractical use.

With the increase in the proportion of the component B used, so risesthe glass transition temperature. However, too high a glass transitiontemperature makes processing of the resin difficult and also leads tothe increase of birefringence refraction, an important opticalcharacteristic. Conversely, when the proportion of the component C islarge, the glass transition temperature is not sufficiently high and thereduction in birefringence attainable is not so marked considering theunsatisfactory glass transition temperature.

In the present invention, besides the components A and B or thecomponents A, B and C mentioned above, other cycloolefins capable ofring-opening polymerization may be used within the range notsubstantially deleterious to the effect of the present invention.Specific examples of cycloolefins which may be used are compounds havingone reactive double bond, such as cyclopentene, cyclooctene, and5,6-dihydrodicyclopentadiene.

Polycyclic norbornene or allied monomers contain as impurities compoundshaving two or more double bonds. Such compounds are preferably removedas completely as possible since they are apt to cause gelation of thepolymer.

The monomer mixture used in the present may be prepared by mixing therespective components prepared in advance. Alternately, it may besynthesized directly by heat-treating DCPs with norbornenes, or byheat-treating DCPs with norbornenes in the presence of cyclopentene. Theheat treatment may be effectuated by heating DCPs with norbornenes, orheating these monomers with cyclopentene, in an atmosphere of inert gassuch as nitrogen gas at a temperature of 120°-250° C., preferably150°-230° C. for 0.5-20 hours, preferably 1-10 hours. The treatmentreaction may be conducted either batch-wise or continuously. An inertsolvent may also be present in the reaction system.

Further, besides the components A and B or the components A, B and C,there may be added chain mono-olefins and chain non-conjugateddiolefins, such as butene-1, pentene-1, hexene-1, octene-1, butene-2,pentene-2, and 1,4-hexadiene, within the range of up to about 10% bymole for molecular weight control.

Polymerization Catalyst

The ring-opening copolymer of these monomers are prepared byconventional methods used for polymerization of norbornenes. Aspolymerization catalysts usable herein, there may be mentioned, forexample, compounds of platinum group metals such as ruthenium, rhodium,palladium, osmium, iridium, and platinum (for example, Japanese PatentApplication Kokoku No. 46-14910) or systems comprising compounds oftransition metals, such as titanium, vanadium, molybdenum and tungsten,and organometallic compounds of metals of the groups I-IV of theperiodic table. Said catalytic systems may be used also in combinationwith a third component such as tertiary amines, etc. (for example,Japanese Patent Application Kokoku Nos. 41-20111, 57-17883, and 57-61044and Japanese Patent Application Kokai Nos. 54-86600 and 58-127728).

The polymerization catalyst is not particularly restricted so long as itis a metallic compound capable of effecting ring-opening polymerizationof the monomers mentioned above. Preferred are, however, catalyticsystems comprising transition metal compounds such as titaniumtetrahalides and organometals such as organo-aluminum compounds, orcatalytic systems comprising said systems and a third component such asaliphatic or aromatic tertiary amines incorporated thereinto.

Specific examples of the polymerization catalyst will be describedbelow.

Transition Metal Compound

Preferred metal compounds are those of transition metals such astitanium, vanadium, tungsten and molybdenum. More specifically, theremay be cited the halides, oxyhalides, oxides, carbonyl compounds andorganic ammonium salts of these transition metals.

As specific examples, there may be mentioned TiCl₄ , TiBr₄ , VOCl₃ ,VOBr₃ , WBr₂ , WBr₄ , WBr₆ , WCl₂ , WCl₄, WCl₅, WCl₆, WF₄, WI₂, WI₄,WOBr₄, WOCl₄, WOF₄, MoBr₂, MoBr₃, MoBr₄, MoCl₄, MoCl₅ , MoF₄ , MoOCl₄ ,MoOF₄ , WO₂, H₂ WO₄, Na₂ WO₄, K₂ WO₄, (NH₄ )₂ WO₄, CaWO₄, CuWO₄, MgWO₄,(CO)₅ WC (OCH₃ ) (CH₃ ), (CO)₅ WC (OC₂ H₅ ) (CH₃ ), (CO)₅ WC(OC₂ H₅) (C₂H₅), (CO)₅ MoC(OC₂ H₅) (CH₃), (CO)₅ Mo═C(OC₂ H₅) (N(C₂ H₅)₂),tridecylammonium molybdate, tridecylammonium tungstate, etc.

Organometallic Compound

Organometallic compounds which may be used include those of the groupsI-IV of the periodic table, for example, organoaluminum compounds,organotin compounds, or compounds of lithium, sodium, magnesium, zinc,cadmium, boron, etc.

Specific examples of the organoaluminum compound includetrimethylaluminum, triethylaluminum, tri-n-propylaluminum,triisopropylaluminum, triisobutylaluminum, trihexylaluminum,trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminummonochloride, di-n-propylaluminum monochloride, diisobutylaluminummonochloride, di-n-butylaluminum monochloride, diethylaluminummonobromide, diethylaluminum monoiodide, diethylaluminum monohydride,di-n-propylaluminum monohydride, diisobutylaluminum monohydride,methylaluminum sesquichloride, ethylaluminum sesquibromide,isobutylaluminum sesquichloride, ethylaluminum dichloride, ethylaluminumdibromide, propylaluminum dichloride, isobutylaluminum dichloride,ethylaluminum dibromide, and ethylaluminum diiodide.

Specific examples of the organotin compound include tetramethyltin,diethyldimethyltin, tetraethyltin, dibutyldiethyltin, tetrabutyltin,tetraisocumyltin, tetraphenyltin, triethyltin fluoride, triethyltinchloride, triethyltin bromide, triethyltin iodide, diethyltindifluoride, diethyltin dichloride, diethyltin dibromide, diethyltindiiodide, ethyltin trifluoride, ethyltin trichloride, ethyltintribromide, and ethyltin triiodide. As other examples, mention may bemade of n-butyllithium, n-pentylsodium, methylmagnesium iodide,ethylmagnesium bromide, methylmagnesium bromide, n-propylmagnesiumchloride, t-butylmagnesium chloride, allylmagnesium chloride,diethylzinc, diethylcadmium, trimethylboron, triethylboron andtri-n-butylboron.

Third Component

A third component may be added to the catalytic system mentioned aboveto enhance the polymerization activity and improve the selectivity inring-opening polymerization. As specific examples, mention may be madeof molecular oxygen, alcohols, ethers, peroxides, carboxylic acids, acidanhydrides, acid chloride, esters, ketones, nitrogen-containingcompounds, sulfur-containing compounds, halogen-containing compounds,molecular iodine, and further Lewis acids, etc. Particularly preferredamong them are aliphatic or aromatic tertiary amines, specific examplesof which include triethylamine, dimethylaniline, tri-n-butylamine,pyridine and α-picoline.

Solvent

The polymerization of the ring-opening copolymer used in the presentinvention may be carried out without using a solvent, but it can beconducted also in an inert organic solvent.

Specific examples of the solvent include aromatic hydrocarbons such asbenzene, toluene and xylene, aliphatic hydrocarbons such as n-pentane,hexane and heptane, alicyclic hydrocarbons such as cyclohexane,halogenated hydrocarbons such as methylene dichloride, dichloroethane,dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, andtrichlorobenzene, etc. These solvent may be used also as a mixture oftwo or more thereof.

Polymerization Temperature

Though the temperature of the ring-opening copolyemrization is notcritical, it is usually selected as desired from the range of-20° C. to100° C.

Polymerization Pressure

The polymerization pressure is preferably selected usually from therange of 0-50 kg/cm .

Hydrogenation

The ring-opening hydrogenated copolymer of the present invention can beobtained by hydrogenating the ring-opening copolymer mentioned above tosaturated a part or the whole of its olefinic unsaturated groups (i.e.,the double bonds of the main chain and the double bonds of theunsaturated ring), whereby the resistance to thermal degradation and theresistance to photo-degradation of the polymer can be improved further.The hydrogenation rate ranges theoretically from 0-100%, the casewherein all of the double bonds of the ring-opening polymer have beensaturated by hydrogenation being taken as 100%, and can actually beselected as desired in said range. To enhance the resistance to thermaldegradation and the resistance to photo-degradation, however, at least50% of the main chain double bonds should be hydrogenated.

The hydrogenation of the ring-opening copolymer is conducted byconventional methods. The hydrogenation catalysts which can be used maybe those generally used in hydrogenation of olefinic compounds and arenot particularly restricted. Examples thereof are as follows. Asexamples of heterogeneous catalysts, there may be mentioned nickel,palladium, and platinum or solid catalysts comprising these metalssupported on a carrier such as carbon, silica, diatomaceous earth,alumina and titanium oxide, e.g., nickel/silica, nickel/diatomaceousearth, palladium/carbon, palladium/silica, palladium diatomaceous earthand palladium/alumina. As examples of homogeneous catalysts, there maybe mentioned those based on metals of the group VIII of the periodictable, for example those comprising a Ni or Co compound and anorganometallic compound of metals of the groups I-III of the periodictable, such as nickel naphthenate/triethylaluminum, cobaltoctenoate/n-butyllithium and nickel acetylacetonate/triethylaluminum, orRh compounds.

The hydrogenation is conducted either in a homogeneous system or in aheterogeneous system according to the kind of catalyst. Though theconditions for hydrogenation may vary depending on the kind of catalyst,it is usually conducted under a hydrogen pressure of about 1-150 atmusually at 0°-250° C., preferably at 20°-180° C. Although the rate ofhydrogenation may be controlled as desired by varying the hydrogenpressure, reaction temperature, reaction time, catalyst concentrationetc., it is necessary for obtaining hydrogenation products exhibitingexcellent resistance to thermal degradation and resistance tophoto-degradation to hydrogenate at least 50%, preferably at least 80%,more preferably at least 90%, of the main chain double bonds in thepolymer.

Ring-Opening Hydrogenated Copolymer

The ring-opening copolymer used in the present invention has anintrinsic viscosity [η] determined in toluene at 25° C. of 0.01-20 dl/g,preferably 0.1-10 dl/g. Similarly, the ring-opening hydrogenatedcopolymer of the present invention has a [η] of 0.01-20 dl/g, preferably1 0.1-10 dl/g. The hydrogenation products, having a [η] in said range,have good thermal resistance, water resistance, transparency, chemicalresistance, solvent resistance, processability and mechanicalproperties.

Ring-opening hydrogenated polymer products obtained by hydrogenation ofring-opening copolymers of TCDs with NBs have a relatively high glasstransition temperature and excellent thermal resistance but, on theother hand, have a problem of rather unsatisfactory birefringence value.As contrasted thereto, in the ring-opening hydrogenated copolymer of thepresent invention, the glass transition temperature of the polymer canbe controlled appropriately to obtain a good balance between thermalresistance and processability and, at the same time, moldings withlittle of optical strain can be obtained even in the region of highglass transition temperatures, by copolymerizing in specified ratios thecomponent A (PCDEs, PCPDs), the component B (TCDs) and, as desired, thecomponent C (DCPs, HDCPs, NBs).

More specifically, the glass transition temperature (Tg) of thehydrogenation products of the present invention can De controlled asdesired in the range of about 110° C.-about 190° C., preferably 170°C.-180° C. in the first aspect and 120° C.-160° C. in the second aspect.

As is apparent from the measured value of bending strength inparticular, the hydrogenation products according to the first aspect ofthe present invention have a mechanical strength equal to or higher thanthat of the ring-opening hydrogenated polymers of TCDs.

As is apparent from the birefringence value, moldings with little ofoptical strain can be obtained even in the region of high Tgs.

Moreover, the hydrogenation products exhibit excellent balance amonglight transmission, water resistance, chemical resistance, solventresistance and mechanical strength. Accordingly, they are suitableparticularly as optical materials.

Further, the ring-opening hydrogenated polymers of the present inventionhave a still more improved resistance to thermal degradation andresistance to photo-degradation as compared with the ring-openingcopolymer used therefor.

Processing

The ring-opening hydrogenated copolymer of the present invention can beprocessed by known methods. Various additives may be added thereto inprocessing, including inorganic and organic fillers, stabilizers,antistatic agents, lubricants, etc.

Uses

The ring-opening hydrogenated copolymer of the present invention has ahigh glass transition temperature and, as is apparent from the fact thatthe unsaturated groups in the original copolymer have been hydrogenated,are excellent in resistance to thermal degradation and photo-degradationand in optical properties and well-balanced among transparency, waterresistance, chemical resistance and mechanical properties, so that it isuseful in a wide field as various formed articles.

Thus, it can be used in a variety of fields including, for example,optical fields, e.g., for optical lenses, optical disks, optical fibers,pellicles and glass windows; electric field, e.g., for water tanks ofelectric irons, electronic oven parts, substrates, for liquid crystaldisplay, printed boards circuit boards for high frequency waves, andtransparent electroconductive sheets and film; medical and relatedfields, e.g., for injectors, pipets and animal cages; and further forcamera bodies, housings of various measuring instruments, films, sheetsand helmets.

EXAMPLE

The present invention will be described in more detail below withreference to Examples and Comparative Examples, but it is in no waylimited to these Examples. In the following description, "part" means"part by weight" unless otherwise specified.

Example 1

In a reactor thoroughly dried and purged with nitrogen, were placed 40parts of pentacyclopentadecadiene (PCDE), 60 parts of tetracyclododecene(TCD), 1% by mole of 1-hexane relative to the total amount (100 parts)of monomers, and 300 parts of toluene. Then 16 parts of 1 molarconcentration toluene solution of triethylaluminum, 4 parts oftriethylamine and 3 parts of 1 molar concentration toluene solution oftitanium tetrachloride were added thereto and the resulting mixture wasallowed to react at 25° C. for 2 hours.

The reaction solution was poured into an acetone/isopropyl alcohol(volume ratio: 1/1, the same applies hereinafter) mixture to coagulatethe polymer, and then the precipitate was separated by filtration anddried to obtain 62 parts of polymer. The yield was 62%.

Analysis of the polymer obtained above by proton NMR spectrometry gave amolar ratio of the PCDE component to the TCD component in the polymer of34:66. The intrinsic viscosity determined in toluene at 25° C. was 0.67dl/g.

Separately, 50 parts of the above polymer was dissolved in 450 parts ofcyclohexane and subjected to hydrogenation using 5 parts ofpalladium-carbon catalyst at a hydrogen pressure of 80 kg/cm² and atemperature of 140° C. for 4 hours. The polymer solution thus obtainedwas filtered to remove the catalyst, then poured into anacetone/isopropyl alcohol (1/1) mixture to effect coagulation, and theprecipitate was filtered and dried to obtain 40 parts of a polymer.

Analysis of the polymer by ¹ H-NMR spectrometry showed that theabsorption of proton due to double bond has disappeared. Thus it wasconfirmed that the polymer had been hydrogenated nearly completely(namely, hydrogenation rate: 100%).

The intrinsic viscosity of the hydrogenated polymer was 0.66 dl/g asdetermined in toluene at 25° C. The glass transition temperature of thehydrogenated polymer determined by DSC analysis was 174° C.

The hydrogenated polymer was compression-molded at 230° C. to prepareplates 10 cm in diameter and 2 mm in thickness. The molded plate wastough and had a bending strength (determined according to ASTM D790) of810 kg/cm². The moisture absorption after immersion in water at 25° C.for 24 hours was 0.1% or less.

The above results reveal that the ring-opening copolymer hydrogenationproduct of the present invention is excellent in thermal resistance andmechanical properties and further is satisfactory in other propertiesincluding water resistance.

Examples 2-4

Ring-opening copolymerization, hydrogenation and compression moldingwere conducted in the same manner as in Example 1 except that themonomer composition was altered to the compositions shown in Table 1(Experiment Nos. 2-4).

The polymers and the compression-molded plates obtained were subjectedto determination of properties in the same manner as in Example 1. Theproperties thus determined are shown in Table 1. The results of Example1 (Experiment No. 1) are also shown in the Table.

Comparative Examples 1-2

For comparison, polymers and plates were obtained and their propertieswere determined in the same manner as in Example 1 except for using asthe monomer PCDE alone or TCD alone. The results thus obtained are shownin Table 1.

As is apparent from Table 1, the ring-opening hydrogenated copolymer ofthe present invention has a high Tg of 170°-180° C. and yet has abending strength in a favorable range of 750-810 (kg/cm²).

Also it has a high water resistance and transparency, and thus is apolymer with well-balanced properties.

                                      TABLE 1                                     __________________________________________________________________________                   Example         Comp. Example                                  Experiment No. 1   2   3   4   1   2                                          __________________________________________________________________________    PCDE (wt %)    40  30  50  60  100 0                                          TCD (wt %)     60  70  50  40  0   100                                        Polymer yield (wt %)                                                                         62  70  63  57  52  63                                         Intrinsic viscosity [η] (dl/g)                                                           0.67                                                                              0.62                                                                              0.68                                                                              0.72                                                                              0.70                                                                              0.64                                       PCDE or PCPD repeating unit                                                                  34  26  44  54  100 0                                          content in polymer (mol %)                                                    TCD repeating unit content in                                                                66  74  56  46  0   100                                        polymer (mol %)                                                               Hydrogenation rate (%)                                                                       100 100 100 100 100 100                                        Intrinsic viscosity [η] (dl/g)                                                           0.60                                                                              0.66                                                                              0.66                                                                              0.72                                                                              0.71                                                                              0.62                                       Glass transition temperature                                                                 174 170 178 180 195 163                                        Tg (°C.)                                                               Bending strenght (kg/cm.sup.2)                                                               810 780 810 750 490 770                                        Light transmittance (%)                                                                      84  85  84  84  83  84                                         (2 mm thick disk, determined                                                  at 830 nm)                                                                    Moisture absorption (wt %)                                                                   <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                                                              <0.1                                       (JIS 6911)                                                                    Solvent resistance                                                            (20 hours, room temp.)                                                        Ethyl acetate  ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                              Acetone        ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                              Chemical resistance                                                           (20 hours, room temp.)                                                        28% aq. ammonia                                                                              ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                              97.6% Sulfuric Acid                                                                          ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                              __________________________________________________________________________     Note: The symbol ∘ in the table indicates that no change          occurred in appearance.                                                  

Example 5

A polymer was synthesized in the same manner as in Example 1 except that20 parts of pentacyclopentadecadiene (PCDE), 35 parts oftetracyclododecene (TCD) and 45 parts of dicyclopentadiene (DCP) wereused. The yield was 70%.

Calculation based on the result of the proton NMR spectrometric analysisof the polymer obtained above and the gas chromatographic analysis ofthe amount of unreacted monomers after polymerization revealed that themolar ratio of the respective components in the polymer originating fromthe PCDE component, TCD component and DCP component were 16:33:51. Theintrinsic viscosity determined in toluene at 25° C. was 0.61 dl/g.

Separately, 50 parts of the above polymer was subjected to hydrogenationin the same manner as in Example 1. The polymer solution thus obtainedwas filtered to remove the catalyst, then poured into anacetone/isopropyl alcohol (1/1) mixture to effect coagulation, and theprecipitate was collected by filtration and dried to obtain 41 parts ofa polymer.

Analysis of the polymer by proton NMR spectrometry showed that theabsorption of proton due to double bond had disappeared. Thus it wasconfirmed that the polymer had been hydrogenated nearly completely(hydrogenation rate: 100%).

The intrinsic viscosity of the hydrogenated polymer was 0.59 dl/g asdetermined in toluene at 25° C. The glass transition temperature of thehydrogenated polymer determined by DSC analysis was 133° C.

The hydrogenated polymer was injection-molded at 350° C. to prepareoptical disk plattes (φ 13 cm, thickness 1.2 mm) and the lighttransmittance, birefringence value and moisture absorption weredetermined. It was found that the light transmittance was 90%, thedouble refraction value (inner periphery-outer periphery of the opticaldisk plate) was 10-40 nm and the moisture absorption was 0.1% or less.

Solvent resistance and chemical resistance were also observed in thesame manner. No change in appearance was observed in both of the tests.

The results thus obtained are shown in Table 2. As is apparent fromTable 2, it can be seen that the ring-opening copolymer hydrogenationproduct of the present invention is excellent in thermal resistance andoptical properties and further is satisfactory in other propertiesincluding water resistance and solvent resistance.

Examples 6-10

Ring-opening copolymerization, hydrogenation and injection molding wereconducted in the same manner as in Example 5 except that the monomercomposition was altered to the compositions shown in Table 2.

The polymers and the optical disk plates thus obtained were subjected todetermination of properties in the same manner as in Example 5. Theresults are shown in Table 2.

Comparative Examples 3-5

For comparison, polymers and optical disk plates were obtained and theirproperties were determined in the same manner as in Example 5 except forusing as the monomer(s) TCD alone, DCP alone, or TCD and NB. The resultsare shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________               Example                 Comp. Example                                         5   6   7   8   9   10  3    4   5                                 __________________________________________________________________________    PCDE (wt %)                                                                              20  20  15  15  20  40  0    0   0                                 TCD (wt %) 35  65  30  55  70  40  100  85  0                                 DCP (wt %) 45  15  55  30  0   10  0    0   100                               NB (wt %)  0   0   0   0   10  10  0    15  0                                 Yield (wt %)                                                                             70  75  78  68  75  67  60   65  68                                Intrinsic viscosity                                                                      0.61                                                                              0.62                                                                              0.58                                                                              0.60                                                                              0.58                                                                              0.57                                           [η] (dl/g)                                                                PCDE repeating with                                                                      16  17  12  12  16  31  0    0   0                                 content in polymer                                                            (mol %)                                                                       TCD repeating unit                                                                       33  64  25  51  67  39  100  77  0                                 content in polymer                                                            (mol %)                                                                       DCP repeating unit                                                                       51  19  63  37  0   12  0    0   100                               content in polymer                                                            (mol %)                                                                       NB repeating unit                                                                        0   0   0   0   17  18  0    23  0                                 content in polymer                                                            (mol %)                                                                       Hydrogenation rate                                                                       100 100 100 100 100 100 100  100 100                               (%)                                                                           Glass transition                                                                         133 158 125 145 142 138 163  125 93                                temperature Tg (°C.)                                                   Intrinsic viscosity                                                                      0.59                                                                              0.63                                                                              0.59                                                                              0.57                                                                              0.60                                                                              0.59                                                                              0.59 0.63                                                                              0.68                              [η] (dl/g)                                                                Light transmittance                                                                      90  91  91  91  90  92  89   91  91                                (%) (1.2 mm thick                                                             disk, determined at                                                           830 nm)                                                                       birefringence (nm)                                                                       10˜40                                                                       20˜70                                                                       15˜50                                                                       20˜60                                                                       20˜60                                                                       15˜40                                                                       40˜130                                                                       30˜80                                                                       30˜90                       (double pass,                                                                 determined at 633 nm)                                                         Moisture absorption                                                                      0.1>                                                                              0.1>                                                                              0.1>                                                                              0.1>                                                                              0.1>                                                                              0.1>                                                                              0.1> 0.1>                                                                              0.1>                              (wt %) (JIS 6911)                                                             Solvent resistance                                                            (20 hours, room                                                               temperature)                                                                  Ethyl acetate                                                                            ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                      ∘                                                                     ∘                     Acetone    ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                      ∘                                                                     ∘                     Chemical resistance                                                           (20 hours, room                                                               temperature)                                                                  28% Aq. ammonia                                                                          ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                      ∘                                                                     ∘                     97.6% sulfuric acid                                                                      ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                     ∘                                                                      ∘                                                                     ∘                     __________________________________________________________________________     Note: The symbol ∘ in the table indicates that no change          occurred in appearance.                                                  

As is apparent from Table 2, the ring-opening hydrogenated copolymer ofthe present invention has a Tg in a favorable range of 125° to about160° C., shows a good birefringence value even in the region ofrelatively high Tg and is excellent in optical properties. Further, ithas high water resistance and chemical resistance and thus is a polymerwith well-balanced properties.

Industrial Applicability

The novel ring-opening hydrogenated copolymer of the present inventionis excellent in thermal resistance and optical properties and haswell-balanced properties including transparency, water resistance,chemical resistance and solvent resistance. Accordingly it can be usedin a vast variety of fields including the optical field.

We claim:
 1. A polycyclic norbornene or its derivative ring-openinghydrogenated copolymer which comprisesa repeating unit represented bythe following formula or the alkyl-substituted derivative thereof (A)and a repeating unit represented by the following formula or thealkyl-substituted derivative thereof (B), has an intrinsic viscosity of0.01-20 dl/g as determined in toluene at 25° C., and in which at least50% of the (C------C) linkages constituting the main chain are singlebonds ##STR9## wherein ------ represents either a single bond or adouble bond.
 2. A polycyclic norbornene or its derivative ring-openinghydrogenated copolymer according to claim 1 which contains 70-10% bymole of a repeating unit represented by the above formula or thealkyl-substituted derivative thereof (A) and 30-90% by mole of arepeating unit represented by the above formula or the alkyl-substitutedderivative thereof (B).
 3. A polycyclic norbornene or its derivativering-opening hydrogenated copolymer according to claim 1 which furthercontains at least one repeating unit (C) selected from a repeating unitrepresented by the following formula, the alkyl-substituted derivativethereof, a repeating unit represented by the following formula, thealkyl-substituted derivative thereof, or the alkylidene-substitutedderivative thereof ##STR10## wherein ------ represents either a singlebond or a double bond.
 4. A polycyclic norbornene or its derivativering-opening hydrogenated copolymer according to claim 3 which contains85-5% by mole of a repeating unit represented by the above formula orthe alkyl-substituted derivative thereof (A),10-90% by mole of arepeating unit represented by the above formula or the alkyl-substitutedderivative thereof (B) and 5-85% by mole of at least one repeating unit(C) selected from a repeating unit represented by the above formula, thealkyl-substituted derivative thereof, a repeating unit represented bythe above formula, the alkyl-substituted derivative thereof, or thealkylidene-substituted derivative thereof.
 5. A process for producing apolycyclic norbornene or its derivative ring-opening hydrogenatedcopolymer wherein at least 50% of the (C ------C) linkages constitutingthe main chain are single bonds which comprises hydrogenating withhydrogen and by use of a hydrogenation catalyst a part or the whole ofthe olefinic unsaturated groups contained in a polycyclic norbornene orits derivative ring-opening copolymer which containsa repeating unitrepresented by the following formula or the alkyl-substituted derivativethereof (A') and a repeating unit represented by the following formulaor the alkyl-substituted derivative thereof (B'), and has an intrinsicviscosity of 0.01-20 dl/g as determined in toluene at 25° C. ##STR11##wherein ------ represents either a single bond or a double bond.
 6. Aprocess for producing a polycyclic norbornene or its derivativering-opening hydrogenated copolymer according to claim 5 wherein saidcopolymer contains 70-10% by mole of a repeating unit represented by theabove formula or the alkyl-substituted derivative thereof (A') and30-90% by mole of a repeating unit represented by the above formula orthe alkyl-substituted derivative thereof (B').
 7. A process forproducing a polycyclic norbornene and/or its derivative ring-openinghydrogenated copolymer according to claim 5 wherein said copolymerfurther contains at least one repeating unit (C') selected from arepeating unit represented by the following formula, thealkyl-substituted derivative thereof, a repeating unit represented bythe following formula, the alkyl-substituted derivative thereof, and thealkylidene-substituted derivative thereof ##STR12## wherein ------represents either a single bond or a double bond.
 8. A process forproducing a polycyclic norbornene or its derivative ring-openinghydrogenated copolymer according to claim 7 wherein said copolymercontains 85-5% by mole of a repeating unit represented by the aboveformula or the alkyl-substituted derivative thereof (A'),10-90% by moleof a repeating unit represented by the above formula or thealkyl-substituted derivative thereof (B'), and (C) 5-85% by mole of atleast one repeating unit (C') selected from a repeating unit representedby the above formula, the alkyl-substituted derivative thereof, arepeating unit represented by the above formula, the alkyl-substitutedderivative thereof, or the alkylidene-substituted derivative thereof. 9.The process of claim 5, wherein said polycyclic norbornene or itsderivative ring-opening copolymer is polymerized by use of a Ti-basedcatalyst.
 10. The process of claim 6, wherein said copolymer ispolymerized by use of a Ti-based catalyst.
 11. The process of claim 7,wherein said copolymer is polymerized by use of a Ti-based catalyst. 12.The process of claim 8, wherein said copolymer is polymerized by use ofa Ti-based catalyst.
 13. The polycyclic norbornene of claim 2, whichcontains from 60-20 % by mole of said alkyl-substituted derivative (A),and from 40-80 % by mole of said alkyl-substituted derivative (B). 14.The process of claim 6, wherein said polycyclic norbornene contains from60-20 % by mole of said alkyl-substituted derivative (A'), and from40-80 % by mole of said alkyl-substituted derivative (B').
 15. Thepolycyclic norbornene of claim 4, which contains from 70-10% by mole ofsaid alkyl-substituted derivative (A), from 20-80% by mole of saidalkyl-substituted derivative (B), and from 10-70% by mole of saidrepeating unit (C).
 16. The process of claim 8, wherein said polycyclicnorbornene contains from 70-10% by mole of said alkyl-substitutedderivative (A'), from 20-80% by mole of said alkyl-substitutedderivative (B'), and from 10-70% by mole of said repeating unit (C').17. The polycyclic norbornene of claim 1, wherein at least 80% of thedouble bonds in the polymer are hydrogenated and the intrinsic viscosityof the polymer is 0.1-10 dl/g.
 18. The polycyclic norbornene of claim17, wherein at least 90% of the double bonds in the polymer arehydrogenated.
 19. The process of claim 5, wherein at least 80% of thedouble bonds of said polycyclic norbornene are hydrogenated and theintrinsic viscosity of the polymer is 0.1-10 dl/g.
 20. The process ofclaim 19, wherein said at least 90% of the double bonds in the polymerare hydrogenated.
 21. The polycyclic norbornene of claim 1, wherein aT_(g) for said polymer is about 110° C. to about 190° C.
 22. Thepolycyclic norbornene of claim 21, wherein a T_(g) for said polymer isabout 170° C. to about 180° C.
 23. The polycyclic norbornene of claim 3,wherein a T_(g) for said polymer is about 120° to 160° C.